JPH02145571A - Production of 2,2,6,6-tetramethyl-4-oxopiperidine - Google Patents
Production of 2,2,6,6-tetramethyl-4-oxopiperidineInfo
- Publication number
- JPH02145571A JPH02145571A JP63300315A JP30031588A JPH02145571A JP H02145571 A JPH02145571 A JP H02145571A JP 63300315 A JP63300315 A JP 63300315A JP 30031588 A JP30031588 A JP 30031588A JP H02145571 A JPH02145571 A JP H02145571A
- Authority
- JP
- Japan
- Prior art keywords
- acetone
- ammonia
- reaction
- mol
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 121
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000007664 blowing Methods 0.000 claims description 15
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical compound O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 239000007844 bleaching agent Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- PIFBMJMXJMZZRG-UHFFFAOYSA-N 2,2,4,6,6-pentamethyl-1,5-dihydropyrimidine Chemical compound CC1=NC(C)(C)NC(C)(C)C1 PIFBMJMXJMZZRG-UHFFFAOYSA-N 0.000 description 11
- 235000019270 ammonium chloride Nutrition 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogenated Pyridines (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アセトンおよび／またはアセトンの縮合物と
アンモニアから２．２，６，６−テトラメチル−４−オ
キソピペリジンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 2,2,6,6-tetramethyl-4-oxopiperidine from acetone and/or acetone condensate and ammonia.
従来、２，２，６．６−テトラメチル−４−オキソピペ
リジン（別名トリアセトンアミン）の製造方法として、
特公昭６２−４１５０４号には、触媒の存在下アセトン
とアンモニアから６０−１２０℃で、１段階の反応で２
，２゜６．６−テトラメチル−４−オキソピペリジンを
製造する方法が記載されている。しかし、この反応は発
熱反応であるため、反応系の温度が高温になりすぎ、収
率が低下するという難点がある。したがって、この方式
を工業的規模で実施する場合は、温度コントロール（除
熱）が問題となる。Conventionally, as a method for producing 2,2,6,6-tetramethyl-4-oxopiperidine (also known as triacetonamine),
Japanese Patent Publication No. 62-41504 discloses that 2
, 2°6.6-tetramethyl-4-oxopiperidine is described. However, since this reaction is exothermic, it has the disadvantage that the temperature of the reaction system becomes too high and the yield decreases. Therefore, when implementing this method on an industrial scale, temperature control (heat removal) becomes a problem.
また特公昭５９−２９５８９号には、触媒の存在下第１
段目の反応を５〜３５℃で行い、次いでアセトンおよび
／またはアセトンの酸性縮合物を追加して４０〜６０℃
に加熱して第２段目の反応を行う方法が記載されている
。しかし、この方法は反応温度が低いため、いずれの段
階も反応時間が長く、生産性が低いという問題点がある
。Furthermore, in Japanese Patent Publication No. 59-29589, the first
The reaction in the second stage is carried out at 5 to 35°C, and then acetone and/or an acidic condensate of acetone is added and the temperature is increased to 40 to 60°C.
A method is described in which the second stage reaction is carried out by heating to . However, since the reaction temperature is low in this method, the reaction time in each step is long and the productivity is low.
本発明の目的は、上記問題点を解決するため、入手が容
易な化合物を出発原料とし、温度コントロールが簡単で
、反応時間が短く、しかも高収率で２．２，６．６−テ
トラメチル−４−オキソピペリジンを製造する方法を提
案することにある。An object of the present invention is to solve the above-mentioned problems by using an easily available compound as a starting material, easily controlling the temperature, shortening the reaction time, and producing 2,2,6,6-tetramethyl 2.2,6,6-tetramethyl The object of the present invention is to propose a method for producing -4-oxopiperidine.
本発明は、アセトンおよび／またはアセトンの縮合物と
アンモニアとを反応させて２，２，６．６−テトラメチ
ル−４−オキソピペリジンを製造するにあたり、触媒の
存在下で、アセトン／アンモニアの割合がモル比で３〜
】０となるように、アンモニアを吹き込みながら４５〜
５５℃の温度で第１段目の反応を行い、アンモニアの吹
き込みを止め、アセトンおよび／またはアセトンの縮合
物を追加することなく５５〜７０℃の温度で第２段目の
反応を行うことを特徴とする２、２，６．６−テトラメ
チル−４−オキソピペリジンの製造方法である。In the present invention, when producing 2,2,6,6-tetramethyl-4-oxopiperidine by reacting acetone and/or acetone condensate with ammonia, the ratio of acetone/ammonia is determined in the presence of a catalyst. is a molar ratio of 3 to
】While blowing in ammonia so that it becomes 0,
The first stage reaction is carried out at a temperature of 55 °C, the ammonia blowing is stopped, and the second stage reaction is carried out at a temperature of 55-70 °C without the addition of acetone and/or acetone condensates. This is a characteristic method for producing 2,2,6,6-tetramethyl-4-oxopiperidine.
本発明で使用するアセトンおよび／またはアセトンの縮
合物としては、例えばアセトン、メシチルオキシド、ジ
アセトンアルコール、ホロンなどを例示できる。これら
は単独で使用してもよいし、２種以上を混合して使用し
てもよい。Examples of acetone and/or acetone condensates used in the present invention include acetone, mesityl oxide, diacetone alcohol, and holon. These may be used alone or in combination of two or more.
本発明において、出発原料となるアセトンおよび／また
はアセトンの縮合物とアンモニアは、アセトン／アンモ
ニアの割合がモル比で３〜１０、好ましくは４〜６とな
るように反応させる。この場合、アセトンの縮合物はア
セトンに換算してモル比を決める。In the present invention, acetone and/or a condensate of acetone and ammonia, which serve as starting materials, are reacted such that the molar ratio of acetone/ammonia is 3 to 10, preferably 4 to 6. In this case, the molar ratio of the acetone condensate is determined in terms of acetone.
上記出発原料の使用割合を３以上にすることにより、第
２段目の反応でアセトンおよび／またはアセトンの縮合
物を追加するという非効率的な操作を省略し、第１段目
の反応と第２段目の反応を連続して行うことができる。By setting the usage ratio of the above starting materials to 3 or more, the inefficient operation of adding acetone and/or acetone condensate in the second stage reaction can be omitted, and the first stage reaction and The second stage reaction can be carried out continuously.
上記出発原料の使用割合が１０を超えると、１バツチあ
たりの生産性が低下し実用的でない。If the ratio of the starting materials used exceeds 10, the productivity per batch decreases and is not practical.
本発明で使用する触媒としては、プロトン酸またはプロ
トン酸のアンモニウム塩が好ましい。このような触媒と
して、例えば硫酸、硫酸水素アンモニウム、塩化アンモ
ニウムなどを例示できる。The catalyst used in the present invention is preferably a protonic acid or an ammonium salt of a protonic acid. Examples of such catalysts include sulfuric acid, ammonium hydrogen sulfate, and ammonium chloride.
触媒の使用量は、反応系全重量に対して０．５〜２０重
量％、好ましくは２〜ｌＯ重量％が好ましい。触媒は反
応液中にそのまま添加して使用すればよく、均一系（必
要により水に溶解した溶液状態）、不均一系（懸濁状態
）のいずれの形態であってもよい。The amount of catalyst used is preferably 0.5 to 20% by weight, preferably 2 to 10% by weight, based on the total weight of the reaction system. The catalyst may be used by being added to the reaction solution as it is, and may be in either a homogeneous system (a solution state dissolved in water if necessary) or a heterogeneous system (suspension state).
本発明の反応では、過剰のアセトンを溶媒として使用す
るのが好ましいが、他の溶媒を使用してもよい。このよ
うな溶媒としては、例えばメタノール、エタノールなど
の脂肪族低級アルコールを例示できる。このような溶媒
は、（アセトンおよび／またはアセトンの縮合物）／溶
媒の重量比で１〜２０、好ましくは２〜１０の割合で使
用するのが好ましい。In the reaction of the invention, it is preferred to use excess acetone as a solvent, but other solvents may also be used. Examples of such solvents include aliphatic lower alcohols such as methanol and ethanol. Such a solvent is preferably used in a weight ratio of (acetone and/or acetone condensate)/solvent of 1 to 20, preferably 2 to 10.
本発明の反応は、アセトンおよび／またはアセトンの縮
合物とアンモニアとから２．２，４，４．６−ベンタメ
チルー２，３，４．５−テトラヒドロピペリジン（アセ
トニン）を合成する第１段目の反応と、第１段目で生成
したアセトニンを分離精製することなく、第１段目の反
応に引き続いてアセトニンから２，２゜６．６−テトラ
メチル−４−オキソピペリジンを合成する第２段目の反
応からなっている。The reaction of the present invention is the first stage of synthesizing 2,2,4,4,6-bentamethyl-2,3,4,5-tetrahydropiperidine (acetonin) from acetone and/or acetone condensate and ammonia. reaction and a second stage to synthesize 2,2゜6.6-tetramethyl-4-oxopiperidine from acetonin following the first stage reaction without separating and purifying the acetonin produced in the first stage. It consists of eye reactions.
第１段目の反応は、前記アセトンおよび／またはアセト
ンの縮合物と前記触媒および溶媒の混合液に、アンモニ
アを前記割合となるように吹き込みながら、４５〜５５
℃の反応温度で、通常１〜１０時間、好ましくは２〜６
時間、通常１〜１０気圧、好ましくは１〜５気圧の反応
条件で実施する。The first stage reaction is carried out by blowing ammonia into the mixture of the acetone and/or the acetone condensate, the catalyst and the solvent at the above ratio.
℃ reaction temperature, usually 1 to 10 hours, preferably 2 to 6 hours.
The reaction time is generally 1 to 10 atm, preferably 1 to 5 atm.
第１段目の反応においては、アセトニンを生成する発熱
反応が主であるが、反応系にアセトンが過剰に存在する
ため、吸熱反応（２３Ｋｃａｌ／ ｍｏｌ、）であるア
セ１〜ニン→２，２，６．６−テトラメチル−４−オキ
ソピペリジンの反応が併発する。このためアンモニアの
吹き込み速度を制御することにより、時間あたりの発熱
景を抑制し、反応温度を容易に上記範囲に制御すること
ができる。In the first stage reaction, the exothermic reaction that produces acetonin is the main one, but because there is an excess of acetone in the reaction system, the endothermic reaction (23Kcal/mol) is ace1-nin→2,2. , 6.6-tetramethyl-4-oxopiperidine reactions occur simultaneously. Therefore, by controlling the ammonia blowing speed, it is possible to suppress the heat generation per hour and easily control the reaction temperature within the above range.
第１段目の反応は１反応器にアセトン、触媒、溶媒等の
混合物を仕込み、これにアンモニアを吹き込む方法のほ
かに、アセトンおよび／またはアセトンの縮合物と触媒
を一定の割合で連続的にフィードすると同時に、アセト
ンに対して前記割合となるようにアンモニアを吹き込ん
で反応させる方法も採用できる。この場合、系内にアン
モニアに対して過剰のアセトンを常に存在させておくも
のとする。In the first stage, a mixture of acetone, a catalyst, a solvent, etc. is charged into one reactor and ammonia is blown into the reactor, or acetone and/or acetone condensate and a catalyst are continuously added at a fixed ratio. At the same time as feeding, a method may also be adopted in which ammonia is blown into the acetone at the above ratio to cause the reaction. In this case, acetone in excess of ammonia should always be present in the system.
第２段目の反応は、アンモニアの吹き込みを止め、第１
段目の反応に引き続き、アセトンおよび／またはアセト
ンの縮合物を追加することなく、５５〜７０℃という第
１段目より高い反応温度で、通常１〜１０時間、好まし
くは２〜７時間加熱撹拌する反応条件で実施する。この
反応の反応圧力は特に限定されない。この反応により、
アセトニンから２．２，６．６−テトラメチル−４−オ
キソピペリジンが１５〜２５重量％の反応系内濃度で生
成する。In the second stage, the ammonia injection is stopped and the first
Following the reaction in the first stage, heating and stirring is carried out at a reaction temperature of 55 to 70°C, which is higher than the first stage, for usually 1 to 10 hours, preferably 2 to 7 hours, without adding acetone and/or acetone condensate. Carry out the reaction under the following reaction conditions. The reaction pressure for this reaction is not particularly limited. This reaction results in
2,2,6,6-tetramethyl-4-oxopiperidine is produced from acetonin at a concentration in the reaction system of 15 to 25% by weight.
本発明の反応を行うための反応器は特に限定されず、槽
壁、管壁など任意のものが使用できる。The reactor for carrying out the reaction of the present invention is not particularly limited, and any reactor such as a tank wall or a tube wall can be used.
また本発明の反応は、バッチ式、連続式のいずれの方式
により、均一系または不均一系の液相反応として行うこ
とができる。Furthermore, the reaction of the present invention can be carried out as a homogeneous or heterogeneous liquid phase reaction, either batchwise or continuously.
上記の反応により、目的とする２、２，６，６−テトラ
メチル−４−オキソピペリジンを、従来の方法に比べ短
時間で、しかも高収率で製造できる。By the above reaction, the desired 2,2,6,6-tetramethyl-4-oxopiperidine can be produced in a shorter time and with a higher yield than conventional methods.
本発明の方法で製造された２、２，６．６−テトラメチ
ル−４−オキソピペリジンは、例えば蒸留精製などの方
法により精製することができ、純度９８％以上の高純度
の製品とすることができる。The 2,2,6,6-tetramethyl-4-oxopiperidine produced by the method of the present invention can be purified by a method such as distillation purification, and should be a highly purified product with a purity of 98% or more. Can be done.
このようにして製造された２、２，６，６−テトラメチ
ル−４−オキソピペリジンは、高分子安定剤、漂白剤の
原料などに使用できる。The 2,2,6,6-tetramethyl-4-oxopiperidine thus produced can be used as a raw material for polymer stabilizers, bleaching agents, and the like.
本発明によれば、触媒の存在下で、アセトンおよび／ま
たはアセトンの縮合物に４５〜５５℃の温度でアンモニ
アを吹き込みながら第１段目の反応を行い、次いでアン
モニアの吹き込みを止め、アセトンおよび／またはアセ
トンの縮合物を追加することなく、５５〜７０℃の温度
で第２段目の反応を行うようにしたので、入手が容易な
化合物を出発原料とし、温度コントロールが簡単で、反
応時間が短く、シかも高収率で２．２，６．６−テトラ
メチル−４−オキソピペリジンを製造することができる
。According to the present invention, the first stage reaction is carried out in the presence of a catalyst while blowing ammonia into acetone and/or acetone condensate at a temperature of 45 to 55°C, then the blowing of ammonia is stopped, and acetone and The second stage reaction was carried out at a temperature of 55 to 70°C without the addition of an acetone condensate, so easily available compounds were used as starting materials, temperature control was easy, and the reaction time was shortened. 2.2,6.6-tetramethyl-4-oxopiperidine can be produced in a short time and in high yield.
次に本発明の実施例について説明する。 Next, examples of the present invention will be described.
実施例１
１Ｑオートクレーブにアセトン２６１．４ｇ（４，５モ
ル）。Example 1 261.4 g (4.5 mol) of acetone was placed in a 1Q autoclave.
メタノール６１．８ｇ、水１０．および塩化アンモニウ
ム８、Ｏｇ（０，１５モル）を入れ、この混合物に５０
”Ｃでアンモニア１４．０ｇ（０，８２２モル）を、流
速１７０ｍ１２／ｗｉｎ（２５℃）で２時間にわたって
吹き込み、第１段目の反応を行った。この時点で反応液
にはアセトニンがｌ００３重量％、 ２，２，６．６−
’テトラメチルー４−オキソピペリジン（ＴＡＡ）が５
．２重量％含まれていた。アンモニアの吹き込みを止め
て昇温し、６０℃で４時間加熱撹拌し第２段目の反応を
行った。反応終了後、塩化アンモニウムと当モル址の水
酸化ナトリウムを水溶液として反応液に加えて中和し、
ガスクロマトグラフィーで分析した。その結果、Ｔ肩が
７６．７ｇ（０，４９４モル）生成していることが判っ
た。使用したアンモニア基準の収率は６０．１モル％、
消費されたアセトン基準の収率は６０．１モル％であっ
た。Methanol 61.8g, water 10. and ammonium chloride 8,0g (0.15 mol), and to this mixture 50
14.0 g (0,822 mol) of ammonia was blown in at a flow rate of 170 ml/win (25°C) for 2 hours to carry out the first reaction. At this point, the reaction solution contained 1003 weight of acetonin. %, 2,2,6.6-
'Tetramethyl-4-oxopiperidine (TAA) is 5
．． It contained 2% by weight. The blowing of ammonia was stopped, the temperature was raised, and the mixture was heated and stirred at 60° C. for 4 hours to carry out the second stage reaction. After the reaction is complete, add ammonium chloride and the same amount of sodium hydroxide as an aqueous solution to the reaction solution to neutralize it.
Analyzed by gas chromatography. As a result, it was found that 76.7 g (0,494 mol) of T shoulder was produced. The yield based on the ammonia used was 60.1 mol%,
The yield based on consumed acetone was 60.1 mol%.
実施例２〜３
実施例１のアンモニアの吹き込み時の温度を５０℃から
第１表に示す温度に変えた以外は実施例１と同様に反応
を行った。結果を第１表に示す。Examples 2 to 3 The reaction was carried out in the same manner as in Example 1, except that the temperature during ammonia injection was changed from 50° C. to the temperature shown in Table 1. The results are shown in Table 1.
第１表
ＴＡＡ：２，２，６．６−テトラメチル−４−オキソピ
ペリジン実施例４
実施例１のアンモニアの吹き込み後の第２段目の反応の
反応温度を６０℃から７０℃に変えた以外は実施例１と
同様に反応を行った。その結果、ＴＡＡ生成量は７６．
０ｇであり、使用したアンモニア基準の収率は５９．６
モル％、消費されたアセトン基準の収率は５７．８モル
％であった。Table 1 TAA: 2,2,6.6-Tetramethyl-4-oxopiperidine Example 4 The reaction temperature of the second stage reaction after blowing in ammonia in Example 1 was changed from 60°C to 70°C. The reaction was carried out in the same manner as in Example 1 except for this. As a result, the amount of TAA produced was 76.
0g, and the yield based on the ammonia used was 59.6
The yield based on mol% and consumed acetone was 57.8 mol%.
実施例５
アセトン２６１．４ｇ（４，５モル）、メタノール６１
．８ｇおよび塩化アンモニウム８．０ｇ（０，１５モル
）からなる混合物に、４５℃でアンモニア２０．５ｇ（
１，２０モル）を流速２４５ｍＡ／ｗｉｎ （２５℃）
で２時間にわたって吹き込み、第１段目の反応を行った
。この時点で反応液にはアセトニンが１８．２重量％、
ＴＡＡが５．７重量％含まれていた。アンモニアの吹き
込みを止めて昇温し、６０℃で４時間加熱還流し第２段
目の反応を行った。Example 5 Acetone 261.4g (4.5 mol), methanol 61
．． 8 g (0.15 mol) of ammonium chloride at 45°C.
1,20 mol) at a flow rate of 245 mA/win (25°C)
Blow was carried out for 2 hours to carry out the first stage reaction. At this point, the reaction solution contained 18.2% by weight of acetonin.
It contained 5.7% by weight of TAA. The blowing of ammonia was stopped, the temperature was raised, and the mixture was heated under reflux at 60° C. for 4 hours to carry out the second stage reaction.
反応終了後、塩化アンモニウムと当モル量の水酸化ナト
リウムを水溶液として反応液に加えて中和し、ガスクロ
マトグラフィーで分析した。その結果、ＴＡＡが７１．
８ｇ生成していることが判った。使用したアンモニア基
準の収率は３８．５モル％、消費されたアセトン基準の
収率は６４．２モル％であった。After the reaction was completed, ammonium chloride and equimolar amounts of sodium hydroxide were added as an aqueous solution to the reaction solution to neutralize it, and the solution was analyzed by gas chromatography. As a result, TAA was 71.
It was found that 8g was produced. The yield based on the ammonia used was 38.5 mol%, and the yield based on the consumed acetone was 64.2 mol%.
実施例６〜７
実施例５のアンモニアの吹き込み時の温度を４５℃から
第２表に示す温度に変えた以外は実施例５と同様に反応
を行った。結果を第２表に示す。Examples 6 to 7 The reaction was carried out in the same manner as in Example 5, except that the temperature during ammonia injection was changed from 45° C. to the temperature shown in Table 2. The results are shown in Table 2.
第２表
ＴＡＡ：２，２，６．６−テトラメチル−４−オキソピ
ペリジン実施例８〜９
実施例１の触媒を塩化アンモニウムから第３表に示す触
媒に代えた以外は実施例１と同様に反応を行った。結果
を第３表に示す。Table 2 TAA: 2,2,6.6-Tetramethyl-4-oxopiperidine Examples 8-9 Same as Example 1 except that ammonium chloride in Example 1 was replaced with the catalyst shown in Table 3. The reaction was carried out. The results are shown in Table 3.
第３表
ＴＡＡ：２，２，６．６−テトラメチル−４−オキソピ
ペリジン実施例１０
１Ｑオートクレーブにアセトン３９２．３ｇ（６，７５
４モル）、水１２．１ｇおよび塩化アンモニウム１２．
０ｇ（０，２２５モル）を入れ、この混合物に５５℃で
アンモニア２１．０ｇ（１，２３モル）を、流速８３ｍ
Ｕ／ｍｉｎ （２５℃）で６時間にわたって吹き込み、
第１段目の反応を行った。この時点で反応液にはアセト
ニンが１２．７重量％、 ２，２，６．６−テトラメチ
ル−４−オキソピペリジン（ＴＡＡ）が６．３重量％含
まれていた。アンモニアの吹き込みを止めて昇温し、６
０℃で６時間加熱撹拌し第２段目の反応を行った。この
後、塩化アンモニウムと当モル量の水酸化ナトリウムを
水溶液として反応液に加えて中和し、ガスクロマトグラ
フィーで分析した。その結果、ＴＡＡが１１１．３ｇ（
０，７１７モル）生成していることが判った。使用した
アンモニア基準の収率は５８．１モル％、消費されたア
セトン基準の収率は５６．２モル％であった。Table 3 TAA: 2,2,6.6-tetramethyl-4-oxopiperidine Example 10 392.3 g of acetone (6,75
4 mol), 12.1 g of water and 12.1 g of ammonium chloride.
0g (0,225 mol) was added to this mixture at 55°C, and 21.0 g (1,23 mol) of ammonia was added at a flow rate of 83 m.
Blow at U/min (25°C) for 6 hours,
The first stage reaction was carried out. At this point, the reaction solution contained 12.7% by weight of acetonin and 6.3% by weight of 2,2,6.6-tetramethyl-4-oxopiperidine (TAA). Stop blowing ammonia and raise the temperature, 6
The second stage reaction was carried out by heating and stirring at 0°C for 6 hours. Thereafter, ammonium chloride and an equimolar amount of sodium hydroxide were added as an aqueous solution to the reaction solution to neutralize it, and the solution was analyzed by gas chromatography. As a result, TAA was 111.3g (
It was found that 0,717 mol) was produced. The yield based on the ammonia used was 58.1 mol%, and the yield based on the consumed acetone was 56.2 mol%.
実施例１１
実施例１０のアンモニアの吹き込み時の温度を５゜°Ｃ
に変えた以外は実施例１０と同様に反応を行った。Example 11 The temperature when blowing ammonia in Example 10 was set to 5°C.
The reaction was carried out in the same manner as in Example 10, except that .
その結果、ＴＡＡ生成社は１０８．０ｇ（０，６９６モ
／Ｌ／） テあり、使用したアンモニア基準の収率は５
６．４モル％、消費されたアセトン基準の収率は５４．
０モル％であった。As a result, the TAA production yield was 108.0g (0,696 mo/L/), and the yield based on the ammonia used was 5.
6.4 mol%, yield based on consumed acetone was 54.
It was 0 mol%.
実施例１２
実施例１０のアンモニアの流速を１６７ｍＱ／ｍｉｎ
（２５℃）に、また吹き込み時間を３時間に変えた以外
は実施例１０と同様に反応を行った。その結果、ＴＡＡ
生成量はｌｌＯ，３ｇ（０，７１１モル）であり、使用
したアンモニア基準の収率は５７．６モル％、消費され
たアセトン基準の収率は５６．２モル％であった。Example 12 The flow rate of ammonia in Example 10 was set to 167 mQ/min.
The reaction was carried out in the same manner as in Example 10, except that the temperature was changed to (25° C.) and the blowing time was changed to 3 hours. As a result, T.A.A.
The amount produced was 110,3 g (0,711 mol), the yield based on the ammonia used was 57.6 mol%, and the yield based on the acetone consumed was 56.2 mol%.
実施例１３
１αオートクレーブにアセトン３９２．３ｇ （６，７
５４モル）、水１２．１ｇおよび塩化アンモニウム１２
．０ｇ（０，２２５モル）を入れ、この混合物に５０℃
でアンモニア２１．Ｏｇ（１，２３モル）を流速１６７
ｍＱ／ｍ１ｎ（２５℃）で３時間にわたって吹き込み、
第１段目の反応を行った。この時点で反応液にはアセト
ニンが１６．７重量％、ＴＡＡが０．８重量％含まれて
いた。アンモニアの吹き込みを止めて昇温し、６０℃で
５時間加熱撹拌し第２段目の反応を行った。この後、塩
化アンモニウムと当モル量の水酸化ナトリウムを水溶液
として反応液に加えて中和し、ガスクロマトグラフィー
で分析した。その結果、ＴＡＡが１０１．２ｇ（０，６
５２モル）生成していることが判った。使用したアンモ
ニア基準の収率は５２．９モル％、消費されたアセトン
基準の収率は５４．８モル％であった。Example 13 392.3g of acetone (6,7
54 mol), 12.1 g of water and 12 ammonium chloride
．． 0 g (0,225 mol) was added to this mixture at 50°C.
So ammonia 21. Og (1,23 mol) at a flow rate of 167
Blow at mQ/m1n (25°C) for 3 hours,
The first stage reaction was carried out. At this point, the reaction solution contained 16.7% by weight of acetonin and 0.8% by weight of TAA. The blowing of ammonia was stopped, the temperature was raised, and the mixture was heated and stirred at 60° C. for 5 hours to carry out the second stage reaction. Thereafter, ammonium chloride and an equimolar amount of sodium hydroxide were added as an aqueous solution to the reaction solution to neutralize it, and the solution was analyzed by gas chromatography. As a result, TAA was 101.2g (0,6
52 mol) was found to be produced. The yield based on the ammonia used was 52.9 mol%, and the yield based on the consumed acetone was 54.8 mol%.
実施例１４〜１５
実施例１３のアンモニアの吹き込み量を２１．０ ｇか
ら第４表に示す量に変えた以外は実施例１３と同様に反
応を行った。結果を第４表に示す。Examples 14-15 The reaction was carried out in the same manner as in Example 13, except that the amount of ammonia blown in was changed from 21.0 g to the amount shown in Table 4. The results are shown in Table 4.
第４表 実施例１６ 温度を４５℃に保った反応容積１５０ｍＱの第１槽に。Table 4 Example 16 In the first tank with a reaction volume of 150 mQ, the temperature was maintained at 45°C.
アセトン−メタノール溶液（重量比４．２：１）を１時
間あたり５０ｍＱ（１時間あたりアセトン３２．３ｇ（
０，５５６モル）〕、アンモニアを１時間あたり２．５
ｇ（０，１４６モル）、および塩化アンモニウムを１時
間あたり１．０ｇ（０，０１９モル）の割合でフィード
し、溢流液を反応容積１５０ｍ１２の第２４１ｆｆに導
き、加熱還流した。ガスクロマトグラフィー分析の結果
、フィード開始１２時間後の第１槽からの溢流液には、
アセトニンが１２．５重量％、ＴＡＡが８．４重量％含
まれており、また第２槽からの溢流液には、アセトニン
が２．３重量％、ＴＡＡが１９．５重量％含まれている
ことが判った。Add acetone-methanol solution (weight ratio 4.2:1) to 50 mQ per hour (32.3 g of acetone per hour).
0,556 mol)], 2.5 mol of ammonia per hour
g (0,146 mol) and ammonium chloride at a rate of 1.0 g (0,019 mol) per hour, the overflow was led to the 241ff with a reaction volume of 150 m12 and heated to reflux. As a result of gas chromatography analysis, the overflow from the first tank 12 hours after the start of feeding contained:
Contains 12.5% by weight of acetonin and 8.4% by weight of TAA, and the overflow from the second tank contains 2.3% by weight of acetonin and 19.5% by weight of TAA. It turned out that there was.
Claims (1)
モニアとを反応させて２，２，６，６−テトラメチル−
４−オキソピペリジンを製造するにあたり、触媒の存在
下で、アセトン／アンモニアの割合がモル比で３〜１０
となるように、アンモニアを吹き込みながら４５〜５５
℃の温度で第１段目の反応を行い、アンモニアの吹き込
みを止め、アセトンおよび／またはアセトンの縮合物を
追加することなく５５〜７０℃の温度で第２段目の反応
を行うことを特徴とする２，２，６，６−テトラメチル
−４−オキソピペリジンの製造方法。(1) Reacting acetone and/or acetone condensate with ammonia to produce 2,2,6,6-tetramethyl-
In producing 4-oxopiperidine, in the presence of a catalyst, the molar ratio of acetone/ammonia is 3 to 10.
45 to 55 while blowing in ammonia so that
The first stage reaction is carried out at a temperature of 55 to 70 °C, the ammonia blowing is stopped, and the second stage reaction is carried out at a temperature of 55 to 70 °C without adding acetone and/or acetone condensate. A method for producing 2,2,6,6-tetramethyl-4-oxopiperidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63300315A JPH02145571A (en) | 1988-11-28 | 1988-11-28 | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63300315A JPH02145571A (en) | 1988-11-28 | 1988-11-28 | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02145571A true JPH02145571A (en) | 1990-06-05 |
Family
ID=17883301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63300315A Pending JPH02145571A (en) | 1988-11-28 | 1988-11-28 | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02145571A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2706056A1 (en) | 2012-09-07 | 2014-03-12 | Evonik Industries AG | Method for the preparation and treatment of a reaction mixture containing triacetonamine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5488275A (en) * | 1977-12-21 | 1979-07-13 | Adeka Argus Chem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPS62212365A (en) * | 1986-03-13 | 1987-09-18 | Mitsubishi Petrochem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPS62212366A (en) * | 1986-03-13 | 1987-09-18 | Mitsubishi Petrochem Co Ltd | Production 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPS62212364A (en) * | 1986-03-13 | 1987-09-18 | Mitsubishi Petrochem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPH01233272A (en) * | 1988-03-11 | 1989-09-19 | Mitsubishi Petrochem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
-
1988
- 1988-11-28 JP JP63300315A patent/JPH02145571A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5488275A (en) * | 1977-12-21 | 1979-07-13 | Adeka Argus Chem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPS62212365A (en) * | 1986-03-13 | 1987-09-18 | Mitsubishi Petrochem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPS62212366A (en) * | 1986-03-13 | 1987-09-18 | Mitsubishi Petrochem Co Ltd | Production 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPS62212364A (en) * | 1986-03-13 | 1987-09-18 | Mitsubishi Petrochem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
| JPH01233272A (en) * | 1988-03-11 | 1989-09-19 | Mitsubishi Petrochem Co Ltd | Production of 2,2,6,6-tetramethyl-4-oxopiperidine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2706056A1 (en) | 2012-09-07 | 2014-03-12 | Evonik Industries AG | Method for the preparation and treatment of a reaction mixture containing triacetonamine |
| DE102012215900A1 (en) | 2012-09-07 | 2014-05-15 | Evonik Industries Ag | Process for the preparation and processing of a triacetonamine-containing reaction mixture |
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